CARBOHYDRATE

RESEARCH

ELSEVIER Carbohydrate Research 305 (1998) 1-15

Thermal decomposition of ascorbic acid 1

Gaston Vernin a,*, Soundouss Chakib a, Sonia M. Rogacheva b, Tzvetan

D. Obretenov b, Cyril P(trk~nyi c
a Laboratoire de Chimie des Ar~mes-Oenologie (C.N.R.S.-URA 1411), Facult£ des Sciences et
Techniques de Saint-J£rbme, Universit~ d'Aix-Marseille III, Avenue
Escadrille-Normandie-Ni£men-Case 561, F-13397 Marseille C[dex 20, France
b Department of Organic Chemistry, Higher Institute of Food and Flavor Industries, P. Hilendarski
University, 26, Boulevard Maritza, BG-4000 Plovdiv, Bulgaria
c Department of Chemistry and Biochemistry, Florida Atlantic University, 777 Glades Road, P.O. Box
3091, Boca Raton, FL 33431-0991, USA

Received 21 November 1996; accepted in revised form 30 April 1997

Abstract

Thermal degradation of L-ascorbic acid at 300 °C in the absence of a solvent yielded

mostly furan derivatives and mr-unsaturated cyclic ketones with a five-membered ring.
Some of the furan derivatives are the same as those obtained in the Maillard reaction, with the
reductones undergoing retroaldol reaction, decarboxylation, oxidation, and hydrolysis. In
propylene glycol, under milder conditions (180 °C), the carbonyl and dicarbonyl derivatives
resulting from the decomposition react with the solvent and give cyclic acetals and ketals
(1,3-dioxolanes). The products were identified by G C - M S using the SPECMA data bank.
© 1998 Elsevier Science Ltd.

Keywords: Ascorbic acid; Thermal degradation; GC-MS analysis; Furan derivatives

1. Introduction enzymes necessary for its biosynthesis and hence

L-Ascorbic acid (1, further referred to as ascorbic
acid) is a well-known natural antioxidant and vitamin
(vitamin C) which is widely distributed in nature,
especially in green plants. It is also synthesized in the
liver of most vertebrates (such as rats). However,
humans, monkeys, and guinea pigs do not possess the
* Corresponding author. Fax: 334 91 28 82 34
1 Presented, in part, at the 21 lth National Meeting of the
American Chemical Society, New Orleans, LA, USA,
March 24-28, 1996.
they have to supplement their diets with ascorbic
acid.
Ascorbic acid, the first vitamin to be discovered,
exhibits antiscorbutic properties (prevention of
scurvy). It is used as a food additive, a flour improver
in bakeries, an animal food additive, an antioxidant,
and for the prevention of the common cold, certain
types of cancer, and other diseases. It acts as an
efficient radical inhibitor.
Structurally, ascorbic acid (1) is a sugar acid, a
y-lactone, and an enediol. It is unstable and is easily
oxidized to dehydro-L-ascorbic acid (2). Its function
in the various biochemical reactions is thought to be
related to its activity as a biological oxidation-reduc-

0008-6215/98/$19.00 © 1998 Elsevier Science Ltd. All rights reserved.

PII S 0 0 0 8 - 6 2 1 5 ( 9 7 ) 0 0 2 3 4 - 6
2 G. Vernin et al./Carbohydrate Research 305 (1998) 1-15
tion agent, hydrogen carrier, and flee-radical trap.
The anion of ascorbic acid is resonance-stabilized.
HC) OH O O
I I
OH OH OH OH
1 2
The most important sources of ascorbic acid in the
human diet are various fruits (especially citrus fruits),
vegetables, herbs (parsley), grasses and, to a lesser
extent, meats (liver) [1-3].
Upon heating of these foods, ascorbic acid behaves
in the same fashion as reducing sugars in the Mail-
lard reaction [4-9]. Its degradation products react
with amino acids, peptides, and lipids (or their degra-
dation products) and give rise to a large number of
aromatic and polymeric products (melanoidins) via
nonenzymatic browning reactions.
Kurata and Sakurai showed that degradation of
ascorbic acid in an acidic medium leads to decar-
boxylation, formation of an intermediate 3-deoxy-L-
pentosulose, and subsequent cyclization to furfural
[10]. Later, they reported on the oxidative degrada-
tion of ascorbic acid, identifying furfural, L-threo-
pentos-2-ulose, 3-deoxy-glycero-pentos-2-ulose-l,4-
lactone, and ethylglyoxal as the major products [11].
The Maillard reaction between ascorbic acid and
twenty amino acids was studied at 44 and 72 °C by
Yu et al. [ 12]. Thermal degradation of ascorbic acid
and dehydroascorbic acid results in the formation of
ten substituted furans [ 13]. Spectroscopic studies (IH-,
13C-NMR, and ESR) were used to elucidate the
structure of dehydroascorbic acid and to investigate
its reactions from the physiological point of view
[14].
During concentration of citrus juices on an evapo-
rator, the initial higher temperature leads to oxidation
of ascorbic acid while concentration under dimin-
ished pressure preserves ascorbic acid better [15].
Related studies have dealt with the effect of ascorbic
acid and oxygen on the nonenzymatic browning reac-
tions in orange juice [16,17], and on the oxidation
and degradation of ascorbic acid [18]. Shin and
Feather examined the stability of ascorbic acid under
physiological conditions alone, in the presence of
a-N-formyl-L-lysine at pH 7.0 in a phosphate buffer,
and in the presence of oxygen [19]. Degradation of
the intermediate L-threo-hex-2,3-diulosonic acid
yielded threonic, oxalic, glyceric, and glyoxylic acid.
Other studies have examined the effect of ascorbic
acid and fructose on the nonenzymatic browning of
peeled and crushed tomatoes [20], on the reducing
properties of ascorbic acid in the presence of com-
plex-forming metal ions [21], the kinetics of sulfite
inhibition of browning of ascorbic acid [22], and the
kinetics of formation of threose from ascorbic acid,
dehydroascorbic acid, and L-threo-hex-2,3-diulosonic
acid, in the presence and in the absence of oxygen, at
pH 7.0 and 37 °C [23].
Cysteine hydrochloride exerts a protective effect
upon preservation of ascorbic acid in processed
pineapples and guavas [24]. Related studies have
investigated the variations of ascorbic acid content
and its effect on the quality and stability of pulp
obtained from a single type of fruit or their combina-
tions (guava-citrus, guava-mango, citrus-mango)
[25].
Feather [9] has described the active role of ascor-
bic acid in the Maillard reaction, as a follow-up on
several earlier articles [26,27]. At pH 7.90 and 37 °C,
ascorbic acid is unstable in the presence of oxygen,
even in the absence of compounds with amino groups.
It decomposes with the formation of carbonyl com-
pounds which subsequently react with amines in the
Maillard reaction giving threose, glyceraldehyde, L-
threo-pentosulose, and 3-deoxy-L-glycero-pentosu-
lose [19].
The foregoing survey of the literature demonstrates
an interest in studies of ascorbic acid as a reducing
sugar in the Maillard reaction. These studies were
carried out in an aqueous medium under different
conditions, with the variables including, but not lim-
ited to, pH, temperature, various additives (amino
acids, peptides) and inhibitors (metal ions, sulfites),
and the presence or absence of oxygen and various
oxidizing agents (thermal degradation).
Here, we have investigated the dry thermal degra-
dation of ascorbic acid (without a solvent) at 300 -t- 10
°C and its thermal degradation in propylene glycol (a
food solvent) at 180 °C.
2. Experimental
General methods.--Dry degradation of ascorbic
acid. Ascorbic acid (1, 1.0 g, 5.68 mmol) was heated
at 300 _+ 10 °C in a pyrolyzer, with dynamic entrain-
ing under N 2. The carrier gas (N 2) carried the volatile
components of pyrolysis into three traps where they
 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15 3

were absorbed in Et20 at a temperature below - 2 0 CH3

I
CH 3 CH 2 CH = C - CH = O
°C. The ether solution was filtered through a silica
gel column, the ether was evaporated, and the volatile
degradation products were analyzed by G C - M S (for
conditions, see GC-MS analyses).
Degradation of ascorbic acid in propylene glycol
The mass spectra of the synthesized 1,3-dioxolanes
at 180 °C. Ascorbic acid (1, 3.6 g, 0.0204 mol) was
were identical with their spectra reported in the litera-
added to anhydrous propylene glycol (20 mL, 20.7 g,
ture [29] and the spectra obtained after the reaction of
0.27 mol). The mixture was heated on an oil bath to
ascorbic acid with propylene glycol.
180 °C and stirred for 6 h. No ascorbic acid was
Other acetals and ketals. Other acetals and ketals
detectable by thin-layer chromatography (TLC) after
can be obtained from the corresponding aldehydes
6 h. The mixture was extracted with 7:3, v / v
and ketones in the same fashion as described above
petroleum ether-CHzC12, the extract was dried
but at different temperatures and with different reac-
(Na2SO 4) and quickly filtered through a silica gel
tion times. They can be distilled under diminished
column under diminished pressure. The solvents were
pressure.
removed on a rotary evaporator and the residue was
Analyses.-- Thin-layer chromatography (TLC).
analyzed by GC and GC-MS.
Ready-made silica gel chromatographic plates were
Synthesis of the acetals.--Synthesis of (Z)- and
used to follow the course of the various reactions just
(E)-2-ethyl-4-methyl-l,3-dioxolanes. Propylene gly-
described. The following eluting solvents were used:
col (20 mL, 20.7 g, 0.27 mol) and propanal (19.6
(a) For the degradation of ascorbic acid: 1:1, v / v
mL, 15.8 g, 0.27 mol) were placed in a 100-mL flask
AcOEE-EtOH; (b) for the synthesis of acetals:
and p-toluenesulfonic acid (0.5 g) and anhydrous
petroleum ether or n-hexane for alkyl-1,3-dioxolanes
Na2SO 4 (10 g) were added to remove water formed
(low polarity), 9:1, v / v benzene-EtOH for more
during the reaction. The mixture was refluxed for 6 h
polar compounds. The spots were detected in ultravi-
at 77 °C. After 6 h, no propanal could be detected in
olet light at 254 nm.
the mixture by GC. The mixture was neutralized with
Gas chromatography (GC). Analytical GC separa-
2 M NaOH, the organic layer was separated, washed
tions were performed on an Intersmat IGC 120 FL
with water, dried (Na2SO4), and filtered. The acetals
gas chromatograph fitted with a capillary nonpolar
were distilled at atmospheric pressure between 113-
OV-1 column (50 m X 0.25 mm i.d.) and a flame-
115 °C [28], while the higher-boiling products were
ionization detector. The temperature was pro-
distilled under diminished pressure (20 mm Hg). The
grammed from 70 to 220 °C at 2 ° C / m i n (injected
residue was analyzed by TLC and by GC-MS. The
sample 0.06 /zL; sensitivity $4 or S16). Integrations
G C - M S analysis indicated the presence of three
were carried out with an Intersmat ICR-1B integrator
products: the two isomeric 2-ethyl-4-methyl-l,3-di-
and were not corrected for varying detector re-
oxolanes (3 and 4, Z and E, respectively, total 70%)
sponses.
in a ratio Z:E = 2:1, and 2-methyl-2-pentenal (5,
GC-MS analyses. Mass spectra were recorded on
30%) resulting from the aldol reaction of propanal.
a Ribermag R-10.10 mass spectrometer (quadrupole)
This a,/3-unsaturated aldehyde is clearly more stable
at an ionizing potential of 70 eV. The instrument was
than the corresponding unsaturated acetals which were
coupled to a Delsi 700 gas chromatograph with a
not detected.
nonpolar DB1 column (50 m X 0.35 mm i.d). The
temperature was kept for 5 min at 80 °C and then
j~,. CH3 "CH3 programmed from 80 to 180 °C (or 200 °C) at 3
/ \-'. ° C / m i n and from 200 to 300 °C at 8 °C/min. In the
case of the dry degradation at 300 + 10 °C, the
analyses were performed on a G C - M S P Hewlett-
Packard instrument at an ionizing potential of 70 eV.
The conditions were: helium as the carrier gas (34
m L / s ) , MSD-HP 5971A detector, nonpolar capillary
3 4 OV-1 column (25 m X 0.2 mm X 0.33 /xm), injected
 4 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15

sample volume 3 /.~L, temperature 40 °C for 5 min, Identification. Using our program, the gas-chro-
then programmed from 40 to 240 °C at 6 °C/min and matographic data (Kovfits indices) and the mass spec-
from 240 to 280 °C at 10 °C/min, detector tempera- tra were compared with the information in our GC-
ture 180 °C, interface temperature 280 °C. MS SPECMA data bank. In most cases, this com-

Name: 2-ACETYLFURAN
Mol. formula: C6H602 Mol. wt. ii0 0- 0-0
ist PROPOSED STRUCTURE
t00

I1
0" , . , , . ,I
20 !O CI iO iN tZt tq4 i¢l t$4 t44 tl,II 2qO 2Li

DI = 610
DI - IK a = 0.00% ***** RECORDING No. 88
DI - IK - 0.00% *****
P UNKNOWN
IO0
IO-

4t.
, , ,]3
14-
| :10 ,
0 , , , , , , , , , , , ,
O 100 IH tql tU iN ~ 2~ ~4 tll

PROPOSED STRUCTURE:-4~: NEXT,~--: PREVIOUS, P: RECOPY, RETURN: EXIT

Name: 2-ACETYLFURAN
Mol. formula: C6H602 Mol. wt. Ii0
Origin: WINE
IK = 890 IK = 1480 D I K - 590 Ref.: 0: 0
a p

106 )|

10"

$0"

• )1 LIO

',0"

• ¢7
20'

0
o
I
:~
I 11
,~o
Ih t
¢o
I
1:8

I
so
1
I
)¢

,oo
I
t:,
I J I
t*~
I I [ I
t¢o ~lo
I I
:0o
I I
:20
I t
~o
I
z~o

Electron impact spectrum: 95(100)

II0(50), 39(50), 43(40), 67(30), 68(20), 96(15), III(I0), 82(4)

Fig. 1. GC-MS SPECMA data bank identification of 2-acetylfuran (6). Top spectrum: Reference spectrum of 2-acetylfuran
in the SPECMA data bank, with its molecular weight, molecular formula, and registry number. Middle spectrum: The
unknown. Bottom spectrum: The top spectrum reproduced in detail. Dissimilarity index, DI = 6-10.
 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15 5

puter-executed comparison resulted in a positive compounds were identified, as shown in Table 1,

identification of the respective compounds. An exam-
ple of the identification procedure is shown in Fig. 1.
The dissimilarity index, DI, indicates the degree of
agreement between the respective spectra. When DI
= 00, the spectra are identical. The higher the value
of DI, the more different the spectra. When DI > 25-
50, the spectrum is filed as an ' u n k n o w n ' .
with their respective structures presented in Scheme
1. The identification was accomplished using the
SPECMA data bank. As an example, the procedure is
illustrated for 2-acetylfuran (6) in Fig. 1. In this case,
the dissimilarity index, DI, is 6-10. This indicates a
very good agreement between the respective mass
spectra.

3. Results and discussion

Dry degradation of ascorbic acid at 300 +__10 °C.

- - G C - M S analysis of the reaction mixture. The mix-
~o~COCH~
ture resulting from the thermal degradation of ascor-
bic acid ( 2 - 3 min at 300 + 10 °C) was analyzed by
G C - M S . Out of the 32 separated products, ca. 20 A comparison of the data in Table 1 with the

Table 1
GC-MS SPECMA data bank analysis of volatile products from thermal degradation of ascorbic acid at 300 °C
No. Compound a Scans b Mol wt m/z ~
7 Butanedione 51 86 43 86
8 A cyclic acetal 110 104? 45 73, 43, 103
9 Unidentified 133 69 39, 41, 40
10 Toluene (artifact) 214 92 91 92, 65
11 C5H60 2 436 98 40 39, 41, 69, 98, 44
12 Furfural 490 96 96 95, 39
13 C5H602 634 98 40 55, 98
14 2(or 3)-Methyl-2-cyclopenten- l-one 777 96 67 96, 69
6 2-Acetylfuran 796 110 95 110,67
15 4,5-Dehydro- y-butyrolactone 812 84 55 84, 39
16 2-Hydroxy-2-cyclopenten- 1-one 854 98 98 55, 69
17 4-Methyl-2-cyclopenten- 1-one 999 96 67 96,81,95
18 2-Cyclohexen- 1-one 1017 96 68 96
19 2-Methyltetrahydrofuran-3-one 1070 100 67 96, 81, 95
20 2-Hydroxy-2-cyclohexen-1-one 1105 112 43 44, 55, 100
21 A methyl ketone 1135 114 43 58, 69, 11
22 2-Hydroxy-3-methyl-2-cyclopenten-1-one (cyclotene) 1217 112 112 55, 69, 83
23 C6H 1002 1269 114 114. 55, 69, 85, 86
24 Unidentified 1317 '~ 70 69, 55
25 Furoic acid 1415 112 95 112
26 2-Hydroxy-3-ethyl-2-cyclopenten-1-one 1536 126 126. 56, 83
27 1-(2-Furyl)-2-hydroxy- 1-propanone 1607 140 95 140
28 A furoyl derivative 1651 122 109. 122, 95
29 A methyl ester, and a furan deriv. 1777 - 60 73; 95, 110
30 A furoyl derivative 1906 9 95 71
31 Unidentified 1966 - 97 69, 95
32 2-Furoylfuran 2295 162 95 162
33 Unidentified 2450 ? 43 69, 58
34 Isomer of No. 26 2475 - 97 95, 69
35 BHT (ether antioxidant) 2532 220 205 220
36 Furil (bis-2,2-furoyl) 2675 190 95 110
37 Unidentified 2824 9 95 87, 69
Principal reaction products are furfural (12, = 70%), 2-hydroxy-2-cyclohexen-l-one (20, = 10%), and furoic acid (25,
= 8%). The structures of the most important compounds are shown in Scheme 1.
b Nonpolar column (SE 30, 25 m × 0.35 mm id).
c Principal fragments are arranged in order of decreasing intensity.
6 G. Vernin et al./Carbohydrate Research 305 (1998) 1-15

results obtained by Veli~ek et al. [13] shows that
some of the products identified in our study were the
same, such as furfural (12), 2-acetylfuran (6), furoic
acid (25), and furil (36). On the other hand, we were
able to identify 2-cyclopenten-l-ones (14, 16, 17, 22,
26), 2-cyclohexen-l-one (18) and its 2-hydroxy
derivative (20), 1-(2-furyl)-2-hydroxy-l-propanone
(27), and 2-furoylfuran (32). Twelve compounds
could not have been identified on the basis of their
mass spectra because of the unavailability of the
reference spectra and the absence of molecular ions.
The fragment with m/z 95 for the compound 29,
as well as the fragments with m/z 95 and 97 obtained
in the mass spectra of 31 and 34 seem to suggest
structures with the furoyl and dihydrofuroyl groups,
respectively [ C 4 H 4 0 • C ( O ) - and C 4 H 4 0 •
CH(OH)-, where C 4 H 4 0 = furyl]. However, furoin,
which is a combination of the foregoing two struc-
tures (mol wt 192) has not been found, perhaps
because of its oxidation to furil (36).
In future studies, positive chemical ionization
( P C I / N H 3 or PCI/iso-C4Hlo) may permit the gen-
eration of quasimolecular ions of unidentified prod-
ucts and the determination of their structures.
It is noteworthy that the decomposition products of
ascorbic acid are the same as those found among the
degradation products of reducing sugars (in the pres-
ence or in the absence of amino acids) and in roasted
food products (coffee). The principal reaction product
is furfural (12, ca. 70%, followed by 2-hydroxy-2-
cyclohexen-l-one (20, "-- 10%) and furoic acid (25,
= 8%) which is formed by oxidation of furfural.
Other products are present in smaller amounts.
Mechanism of formation of the principal reaction
products. The suggested mechanism of formation of
the principal reaction products is shown in several

~
~CH3
o

CH3~ , ~
y .CH3
H CH3
O o O O
7 12 14 and 17 6

[ ~CH3 ~ O H
~ R
O O O
16 R = H 18 R = H 19 25

22 R = CH 3 20 R = O H

26 R = C2H s

O O
27 32 36

Scheme 1.
 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15 7

HC-OH
O H J
H II
ICHz".CH'.CH-- .C'--r-q~,.,,, C-OH
H20 I I *'/~ k ~t ~Jn - CO2
la OH OHOH ?) " - \ ---ib,,- I
,....e- C~ HC-OH
H~O/ 0 I
OH OH HO-CH
I
CH2OH
lb

CHO CHO CHO

I I I
C-OH C=O C--O
- H20
- H20 II ~ I I
- H20

CH --.....r--- CH2 CH
I I II f/H
HO-CH HO-CH CH
I I I 0
CH2OH CH2OH CH2OH 12

38 39

Scheme 2.

schemes. Scheme 2 presents the possible formation of
furfural (12) via 3-deoxyopentosulose (38) and 3,4-
dideoxypentos-3-en-ulose (39). However, furfural
(12) can also be formed from hydroxyacetaldehyde
(40) and pyruvaldehyde (41) (Scheme 3). Similarly,
2-acetylfuran (6) results from the condensation of
hydroxyacetaldehyde (40) and butanedione (7)
(Scheme 3). In both cases, the starting materials in
Scheme 3 arise from thermal degradation of dehydro-
ascorbic acid (2). Once formed, furfural (12) can
participate in aldol reactions with other carbonyl
compounds, such as hydroxyacetaldehyde (40).

HO., / H
H--C C ~H

/ \
::) ~.'
H-C = O CH3
i I
H2C-OH O = C-C-R
II
O

40 41 R = H H
7 R=CH 3

HO,,. /H
H--C C -H - 2 H20

." ~ o / % 0 , - O ~ O

12 R = H
6 R=CH 3

Scheme 3.
8 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15

Scheme 4 shows dimerization of hydroxyacetone of water. In a similar fashion, it is possible to explain

(42) and its tautomer leading to the cyclopentene the formation of 4-alkyl-2-hydroxy-l-cyclopenten-1-
derivative 22 by a consecutive loss of two molecules ones from hydroxy a-carbonyl compounds, and (2 H)-

Table 2
Mass-spectral characteristics (electron impact) of the products obtained by degradation of ascorbic acid in propylene glycol
at 180 °ca
No. (listing) b Scans c Mol wt d m/z e
1.2-Substituted 4-methyl-1,3-dioxolanes (different substituents)
4 236 102 87 43,58,51,59
7/8 305/312 116 87 31,41,59,57,72
15/16 571/587 132 87 31,59,41,43
17/18 595/610 132 87 31,43,59,57
30/31 1933/1753 188? 43 87,42,59,31,101
38 / 39 2216/2372 9 87 42,43,57,115,129
40 2396 202? 87 42,43,57, 115,129
41 2490 170? 43 87,95,42, 101,126
49 3223 228? 42 87, 100, 144, 173
52 / 53 3921 / 3960 228 87, 59,56, 114
55 / 56 4281/4329 228 69, 87,42,59, 145,115
57/58 4387/4424 230 69, 42,59,87,145,115
62 / 63 5494/5572 286 87, 187,59
87, 43,56,187
68 / 69 6555/6645 288 87, 85,143,212,59,41,31
2. 2-Substituted 2,4-dimethyl- 1,3-dioxolanes
5 261 118 43,101,42,40,72
14/15 549/571 132 43,101,58,41,31
22/23 798/818 146 43,101,41,87,59
27/28 1571/1802 144 43,101,87,59
29/30 1621/1693 144/146 43,101,41,87,59
3. 1,3-Dioxolanes and other compounds f
19 650 132 57,29,43,87, 102
20 662 132 57,29,43,88,87,102
21 684 132 57,29,43,87,102
25/26 1218/1238 154 95,100,81,154
32/33 1827/1871 188 43,101,87
41 i/42 2490/2564 170 95,43,10
43 1732 202? 71,129,43
44/45 2773/2860 214 100,425
46/47 3001/3092 214 100,42 g
47 3092 228 114,96,41
48/49 3181/3223 214 100,42
48 3181 228 57,115,87,173
51 3741 9 41, 127,69
54/55 4150/4280 280 69,42,59,95
59 4942 224 43,83,57,97,69 h
61 5288 248 95,153
64/65 6282/6392 288 85,87,201 g
66/67 6418/6465 288 85,87,2015
70/71 6804/6852 276-298? 114,56,41,56,127,242,127,187
72 / 73 6906/6980 264? 114,41,56,127,242,187
77/78 7694/7726 290? 151,209,95
79 7993 296 95,151,42,110,173,238
80 9802 298 43,98,57,118,267,298
 G. Vernin et al./ Carbohydrate Research 305 (1998) 1-15 9

HOCH2 .,~ ~ 0 = C-H

[ I /CH3
O~C NCH3 HO/c'"H
42a 42b

CH3
HOCH2 HO-C-H CH 3
I
I I HOCH2 HO-C-H
~C \ ~ / . C I I
O OH3 H %0 o~IC~_ jC-OH
~C/ H
H2

HOCH2 HO-C-CH3 HOCH2 O=C-CH

3
- H20
I II I i
o//C~c/CH C~ /CH 2
(3// - - C - -
H2 H2

[]
I I H3
HO~ C C--CH 3
--,..- / \
o C c/Cm
H2
22

Scheme 4.

Notes to Table 2:
G C - M S analysis was carded out On a nonpolar column DB-1 programmed from 70 to 200 °C at 2 °C/min a n d / o r from
20 to 300 °C at 5 °C min.
b These correspond to the numbers of the spectra in the listing (from 1 to 80). Isomer pairs (Z and E) giving the same mass
spectra are placed together.
Number of scans of mass spectra.
d Observable molecular weights are shown. In the case of 2-substituted 1,3-dioxolanes a very low intensity fragment at
( M - 1)-- or ( M - 15) + can be seen.
e Principal fragments are shown in the order of decreasing intensity.
f The following additional compounds were identified: acetaldehyde (mol wt 44, BP 44), butanedione (mol wt 86, BP 43),
propylene glycol (mol wt 76, BP 45), propionic acid (mol wt 74) in a mixture, furfural (mol wt 96, BP 39), 2-acetylfuran
(mol wt 110, BP 95), C]2 and C14 linear alkanes, dibutyl phthalate, etc.
g Four isomers.
h Hexadecene.
10 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15
o o
( 0 L 0
4 7/8
.o/'.,( o
0
L HO( o
0 L
17/18 14/15
(3
(27/28)*
* Two majorproducts.
Scheme 5. The numbers are listing numbers (Table 2).
and (3H)-4,5-dehydrofuranones by ring enlargement
from 3-methyl-2-cyclopenten-l-ones (14) formed
from glyoxal, CHO. CHO, and butanedione (7) 2.
Thermal degradation of ascorbic acid in propylene
glycol at 180 °C. Dry degradation of ascorbic acid
described above takes place under relatively drastic
conditions. Thermal degradation of ascorbic acid in
propylene glycol at 180 °C, takes place at a tempera-
ture analogous to that used in baking of various
foods. The results were unexpected: Only a few furan
derivatives [e.g., furfural (12), 2-acetylfuran (6)] were
found among the eighty separated products (Table 2).
Most products can be characterized by base peaks at
m/z 87 and 101 and, in some cases, at m/z 115 and
129. These fragments are characteristic of the cations
2 Additional schemes with the proposed mechanisms of
formation of these compounds are available from the
authors.
15/16
OH
22/23
61
based on 2-mono- and 2,2-disubstituted 4-methyl-
1,3-dioxolanes, with the Z- and E-isomers in most
cases.
The products shown in Table 2 are divided into
three groups. The first group (24 compounds) in-
cludes the various 2-substituted 4-methyl-l,4-di-
oxolanes (R ~= H). The second group (15 products)
are most likely 2-substituted 2,4-dimethyl-l,3-di-
oxolanes (R ~ = CH3; m/z 43 and 101). The third and
most important group (37 products) are compounds
which have not been positively identified (no refer-
ence spectra are available). In some cases, four dif-
ferent isomers were observed (for listing nos. 64, 65,
66, 67, and for 70, 71, 72, and 73). Assuming that
these products are substituted 1,3-dioxolanes, they
should contain a double bond in position 2 of the side
chain. The structures of some identified compounds
are presented in Scheme 5. The respective precursors
of these compounds are acetaldehyde (for listing No.
4), propanal (for listing Nos. 7 / 8 ) , 2-hydroxypro-
 G. Vernin et al. / Carbohydrate Research 305 (1998) 1-15 11

panal (listing Nos. 15/16), hydroxyacetaldehyde polymerization. Propanal is formed by dehydration of

(listing Nos. 17/18), hydroxyacetone (listing Nos. propylene glycol:
14/15), acetoin (listing Nos. 22/23), butanedione CH3CH(OH)CHzOH ~ CH3CH=CHOH
(listing Nos. 27/28), and furil (listing No. 61). All
these precursors arise from degradation of ascorbic CH3CH2CHO
acid (Scheme 5). Retroaldol reactions lead to pyru- Aldol reaction of the latter gives 2-methyl-2-
valdehyde, glyoxal, hydroxyacetaldehyde, and 2,3-di- pentenal (5). Acetylation is also one of the processes
hydroxypropanal. to be considered.
Some of these compounds are quite unstable and The two most important reaction products are the
undergo ready oxidation to the respective acids or Z- and E-isomers with the molecular ion with m/z

CH3C~ O +

m/z 43 I
O+
- CH3CH 2

O CH3CH2CH ~ CH2 • CH2=C CH 2

CH2=C~+
/ \o / -oH3
r
NJ
+• I
o H
I
H
m/z 101 (1%) m/z 72 (18%) m/z 57 (29%)

- CH 3 3CHO

o 7;
- CH3CH 2
CH3CH2CH ~ CH3CH2C~o r

+
m/z 42
m/z 116 (0%) m/z 87 (100%)
(resonance stabilized)

I
.H e
-CO

4-
Hc-o + CH3CH = C = OH
m/z 29 (37%) m/z 59 (53%)
O
+

m/z 115 (1%)

CH2OH- 1 + CH3CHOH--] +

m/z 31 (56%) m/z 45

Scheme 6.
12 G. Vernin et al./ Carbohydrate Research 305 (1998) 1-15

144 and an important fragment at m/z 101, character- (listing Nos., Table 2). As an example, Scheme 6
istic of 2-substituted 2,4-dimethyl- 1,3-dioxolanes. It shows the fragmentation of the two isomeric 2-ethyl-
follows from the base peak at m/z 43 ( 1 4 4 - 43 = 4-methyl-l,3-dioxolanes (Z and E, 3 and 4, respec-
101) that the substituent is an acetyl group. Thus, the tively). We have synthesized these two compounds
structures assigned to these products are 27 and 28 and used the G C - M S data for their positive identifi-
Name: (Z)-2-ETHYL-4-METHYL-I,3-DIOXOLANE
Mol. formula: C6H1202 Mol. wt. 116
Origin: VITAMIN C/PROPYLENE GLYCOL; VERNIN & CHAKIB, 1995.
IK = 0 IK = 0 DIK = 0 Ref.: 0: 0
a p

31 ~1 S$

I$
|7
41
41 7Z

I I I
it" I I I I 1
I
i I [ i I I I I I I t I I i i
o Io qo ¢o to too 120 i~O t¢O tOO 290 ~:0 5~0 2¢0

Electron impact spectrum: 87(100)

31(56), 41(53), 59(53), 29(37), 57(29), 42(23), 27(20), 43(18),
72(18), 39(12), 45(11), 58(8), 115(3)

Name: (E)-2-ETHYL-4-METHYL-I,3-DIOXOLANE
Mol. formula: C6H1202 Mol. wt. 116
Origin: VITAMIN C/PROPYLENE GLYCOL; VERNIN & CHAKIB, 1995.
IK a = 0 IKp - 0 DIK - 0 Ref.: O: 0

*°°t
'°t
CO"

+t 5~

2:"

i
i i i I 1 ~ i I 1 I I i 1 I !
o 20 ~o ~o so :oo t:o 1~o ~l;D ~.$0 ZOO 220 ~0 ~60

Electron impact spectrum: 87(100)

31(57), 41(50), 59(48), 29(33), 57(24), 42(21), 72(18), 27(17),
43(17), 45(12), 39(ii), 58(6), 88(5), 115(2)

Fig. 2. Mass spectra of (Z)-2-ethyl-4-methyl-l,3-dioxolane (3) (top) and (E)-2-ethyl-4-methyl-l,3-dioxolane (4) (bottom)
obtained by thermal decomposition of ascorbic acid (1) in propylene glycol.
 G. Vernin et al./ Carbohydrate Research 305 (1998) 1-15 13

cation. The major process in the fragmentation scheme acetaldehyde and the formation of fragments at m/z
is a loss of the ethyl radical in position 2 giving a 72, 57, 43, 42, and 29. Additional low-intensity peaks
base peak at m/z 87. This fragment then gives addi- are observed at m/z 115 (M-H) + and 101 ( M -
tional fragments with m/z 59, 31, and 45. The second CH3) +. The molecular ion is not seen.
important pathway is the ring cleavage with a loss of The formation of acetals is not unexpected.

Name: (Z)-2-ETHI~-4-METHYL-I,3-DIOXOLA~NE
Mol. formula: C6H1202 Mol. wt. 116
Origin: SYNTHETIC (PROPANAL/PROPYLENE GLYCOL); VERNIN & CRAKIB, 1995.
IK = 0 IK = 0 DIK - 0 Ref.: 0: 0
a p

10#,

I0"
31

CO
It

tO

I I
r, i"
I I I I
t
I t
0 lO I0 40 IO tO0 t20 140 Ilia ltO I00 llO l~*O I¢11

Electron impact spectrum: 87(100)

31(70), 59(56), 41(53), 29(50), 57(30), 42(23), 72(22), 43(18),
39(15), 58(8), 71(8), I15(4), I01(I)

Name: (E)-2-ETHYL-4-METHYL-I,3-DIOXOLANE
Mol. formula: C6H1202 Mol. wt. 116
Origin: SYNTHETIC (PROPANAL/PROPYLENE GLYCOL); VERNIN & CRAKIB, 1995.
IK a = 0 IK p = 0 DIK = 0 Ref.: 0: 0

SO"
it

CO"

° [l'i'IF';; I" I
i I I 1 I I I I I I I I I I I i f I I 1 ! ! I I
o 2~ ~¢ 60 lo too 2SO

Electron impact spectrum: 87(100)

31(73), 41(55), 59(55), 29(47), 57(25), 42(23), 72(23), 43(19),
39(15), 71(8), 58(6), 115(3), I01(1)

Fig. 3. Mass spectra of (Z)-2-ethyl-4-methyl-l,3-dioxolane (3) (top) and (E)-2-ethyl-4-methyl-l,3-dioxolane (4) (bottom)
synthesized from propanal and propylene glycol.
14 G. Vernin et al./ Carbohydrate Research 305 (1998) 1-15

MacLeod et al. [29] were the first to describe the alters the characteristic beef flavor because of the
interaction of propylene glycol with carbonyl com- formation of 1,3-dioxolanes [29].
pounds formed in the Maillard reaction and leading Three 1,3-dioxolanes, namely, 2,4-dimethyl-, 2-
to 1,3-dioxolanes. In the beef-flavored commercial isobutyl-4-methyl-, and 2-(1-isopropyl-4-methyl- 1-
products, the use of propylene glycol as the solvent pentenyl)-4-methyldioxolane were identified by Hart-

Name: (Z)-2-ETHYL-4-METHYL-I,3-DIOXOLANE
Mol. formula: C6H1202 Mol. wt. 116
Origin: SIMULATED BEEF FLAVOR; MacLEOD et al., J. AGRIC.
FOOD CHEM., 28 (1980) 4AI.
IK = 0 IK - 0 DIK: 0 Ref.: 0 0
a p

t0¢

$0"
11
It ~t

41

t I I t
I t I I II I I I I I I I I 1 I I
o n , , w tN tn t~ tN tu tN ~ ~ no

Electron impact specerum: 87(100)

59(73), 31(64), ~I(62), 43(31), 57(22), 42(12), 72(7)

Name: (F)-2-ETHYL-4-~nxL-I,3-DIOXOLANE
Mol. formula: C6H1202 Mol. wt. 116
Orlgin: SIMULATED BEEF FLAVOR; MacLEOD et al., J. AGRIC.
FOOD CHEM., 28 (1980) 441.
IKa - 0 I~ - 0 DIK: 0 Ref.: O: 0

*°°! j l.SI

80-
5|

I I I I t I I I I t I I I I I I I I I J
0 tO $~ le N 100 till t~ t~ it0 IN llO ~0 1¢0
Electron impact spectrum: 87(100)
59(72), 31(55), 41(53), 57(22), 42(21), 43(20), 72(12)

Fig. 4. Mass spectra of (Z)-2-ethyl-4-methyl-1,3-dioxolane(3) (top) and (E)-2-ethyl-4-methyl-l,3-dioxolane (4) (bottom) in

simulated beef flavor [29].
 G. Vernin et al./ Carbohydrate Research 305 (1998) 1-15
man et al. [30] among the products of the reaction of
leucine and D-glucose in propylene glycol as the
solvent. The synthesis of 2-formyl-4,5-dimethyl-l,3-
dioxolane was reported by Thiam and Chastrette [31]
using glyoxal and glycerol as the starting materials.
This is the starting material for the synthesis of chiral
acetals. We have not found any 4-methyl derivative
in our reaction mixture.
Kantlehner and Gutbrod [28] described the synthe-
sis of a number of 1-alkyl-4-methyl-1,3-dioxolanes in
the presence of N,N-dimethylformamide and
dimethyl sulfate. Finally, MacLeod et al. [29] carried
out the synthesis of 1,3-dioxolanes using p-toluene-
sulfonic acid and removing the water formed in the
reaction by distillation of an azeotropic mixture with
benzene. The products were purified by distillation
under diminished pressure. An adaptation of this
method was used in our study for the synthesis of
several reference compounds.
An example shown in Fig. 2 presents the mass
spectra of (Z)- and (E)-2-ethyl-4-methyl-l,3-di-
oxolanes synthesized in our laboratory from propanal
and propylene glycol. For comparison, Fig. 3 con-
tains the mass spectra of these two compounds identi-
fied after thermal decomposition of ascorbic acid in
propylene glycol, and Fig. 4 represents their mass
spectra in simulated beef flavor [29]. The agreement
among the three sets of spectra is excellent.
Acknowledgements
The authors thank Mrs. Genevieve M.F. Vernin for
her careful technical assistance.
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